Process for breaking petroleum emulsions



y 1952 M. DE GROOTE 2,602,053

I PROCESS F OR BREAKING PETROLEUM EMULSIONS Filed Aug. 14, 1950 I007, OXYETHYLATED PHENOL-ALDEHYDE RESIN; RATIO OF OXIDE TO RESIN WITHIN THE RANGE OF 4.0 T0 4.8 ON A MOLAL BASIS CALCULATED ON ORIGINAL PHENOLIC HYDROXYL 100% OXYETHYLATED IOOZ, OXYETHYLATED PHENOL-ALDEHYDE PHENOL-ALDEHYDE RESIN; RATIO OF OXIDE RESIN; RATIO OF OXIDE TO RESIN WITHIN THE TO RESIN WITHIN THE RANGE OF 2.0 T0 2.4 RANGE OF 3.0 T0 3.6 ON A MOLAL BASIS ON A MOLAL BASIS CALCULATED ON ORIGINAL CALCULATED ON PHENOLIC HYDROXYL ORIGINAL PHENOLIC HYDROXYL INVENTOR,

Patented July 1, 1952 rtur PROCESS FOR BREAKINGPETRQLEUM EMULSIQNS Melvin De Groote, University City, -Mo., assignor to Petrolite Corporation, Ltd.,Wilmingtn;-Del., ,a corporation of Delaware Application August 14, 1950, Serial 'No. 17.91402 7 Claims. '1 V This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil t pe and particularly petroleum emulsions.

My 'invention provides an economical and rapid process forresolving petroleum emulsions'of the water-in-oil type that are commonly referred-to as cut oil, roily oil, emulsified oil, -etc.,-and-which comprise 'iine droplets of naturally-occurring waters or 'brines-dispersed in amore orless permanent state throughout the oil which constitutes the continuous'phase'of the emulsion.

It also provides an economicaland rapid process for separating emulsions which have been prepared under controlled conditions from'mirrleral oil, such as crude oil and relatively soft watersor weakbrines. Controlled emulsification and subsequent demulsification under the conzditionsjust mentioned are of significant value in removing impurities,particularly inorganic-salts, :frompipeline oil.

Demulsification as contemplated inzthepresent application includes the preventive step of comvlminglingvthe demulsifier with the aqueous component which wouldor might subsequently become either phase of the emulsion in the-absence of such precautionary-measure. Similarly, such demulsifier may be mixed'with the hydrocarbon component.

Reference is'made to U. S. Patent No. 2,499,368.

' This patent is concerned with a process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a ,demulsifier including hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon'atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (-B) an oxyalkylation-susceptible, fusible, organic solwent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction be- :tween a difunctionalmonohydric phenol and an aldehyde havingnot over 8 carbon atoms-and reactive toward said phenol; said resin being i formed in-the substantial absence oftriiunctional phenols; said phenol beingpf the formula u s fie wh ch :in turn :i :a syne is ic ter ry mixture .of'gthree components, each of the ,three in which R --is a hydrocarbon radical having not more than 252 carbon atoms and substituted in the 2, :4, 6 apesitipngsaid oxyallgylated resinbeing characterized by the-introduction into the resin molecule .of ,a plurality :of divalent radicals having the formula (R10) n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxyp op len r i als, and hydr xy uty radicals, and'M -a numer va ine f om 1110 2.0;

with thezpmvisothat etrl a t =mo e e yl oxide be introduced {or :each ,phenolic nucleus.

I have found that if a phenol-aldehyderesinis prepared from a difunctional hydrocarbon-substituted phenol having atleast 4 and not over 18 carbonatoms in the suhstituent radical, and if such ;phenol=-aldehyde resin is treated with ethylene oxide soas'tmobtainthree differentdegrees Qfoxyethylatien as hereinafter described, that a 7 mixture of ,these three ,has a synergistic pr0perty;a a a d mul ifi a i is concerned, insofar that such :mixture is ,more ,effective,, for instance, atlleast;1,0 rmore reflective than any one of' the three components alonecr any .tw sof the threeincombination. Thisapplies provided the =mixture pf the j-three :is within certain proportions, :i. e., at :least 20 and not more than 60% of each ;of the three components. Reference ismade to-thechart ofjthe hereto attached drawing.

Specifically, then, ,the present invention is -;con @c med with jip n ess for breaking p roleum emulsions -;of :the water in-oil type characterized bvsubiecting th emulsipn't theact a :d

components being *a hydrophile synthetic product; saidihydrophile synthetic product-being the oxyethylationproductof -(-A) ethylene oxide, and

(B) an oxyethylation-susceptible, :fusible, organic solvent -soluble, water-insoluble phenolaldehyde resin; said -resin being derived by reaction ;be-

tweena-difu-nctional monohydric phenol and an active toward said phenol; said resin being formed in the substantial absence of trifunctiona1 phenols; said phenol being of the formula divalent radicals having the formula (-C2H4O )n; in one of the three components n varies from 2.0 v

to 2.4 on a molal basis calculated on the original phenolic hydroxyl; in the second component 17. varies from 3.0 to 3.6 on a molal basis calculated on the original phenolic hydroxyl; in the third component it varies from 4 to 4.8 on a molal basis calculated on the original phenolic hydroxyl; the phenolic and aldehydic reactants being identical in all three components; the combining ratios of the three components being determined by the triangular area of the graph in the hereto appended drawing as defined approximately by the triangle A, B, C, said proportions being on a weight basis; and with the final proviso that said demulsifier be more effective than (1) any of the three components alone, or (2) any two ofthe three components in combination.

For convenience, the subsequent subject matter will be divided into four parts:

Part 1 is concerned with the preparation of the phenol-aldehyde resin;

Part 2 is concerned with the oxyethylation oi: the resin;

Part 3"is concerned with the preparation of the mixtures to yield a combination having the synergistic property previously referred to, and

Part 4 is concerned with this mixture for use in demulsification.

PART 1 '7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U.- S. patents: Nos. 2,499,365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having4 to 12 carbon atoms are most ,satisfact0ry,.with the additional C14 carbon atomalso being very satisfactory. The increased cost of the C16 and C18 carbon atom phenol render these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methodsof preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 1030. of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol. suchas the orthoor para-substituted phenol, or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

PART 2 As has been pointed out previously suitable resins can be made following the procedures described or, for that matter, can be purchased in the open market. The second step in the overall procedure involves the use of ethylene oxide.

I have prepared a large number of resins of the kind described in Part 1, preceding, on a laboratory scale varying from a few hundred grams or less to somewhat larger amounts. Needless to say, they are prepared also regularly .on an industrial scale. This same statement applies to the preparation of the oxyethylated products with Y which this second part is concerned. 7

For anumber of well known reasons equipment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scale size, is not as a rule designed for a particular alkylene oxide. Invariably and inevitably, however, and particularly in the case of laboratory equipment the design issuch as to use any of the customarily available alkylene oxides, i. e., ethylene oxide, propylene oxide, 'butylene oxide, glycide, epichlorohydrin, styrene oxide, etc.

oxyethylations, and for that matter oxypropylations, are conducted under a wide variety of conditions not only in regard to presence or absence of catalyst, kind of catalyst subsequently described, but also in regard to time of reaction, temperature of reaction, speed of reaction, pressure during reaction, etc. Oxyalkylations, and particularly oxyethylations, can be conducted at temperatures approximating the boiling point of water or slightly above, as for example to C.

Likewise, resins can be oxyalkylated, particularly with ethylene oxide, using temperatures and pressure which are comparatively high, for instance, temperatures in the neighborhood of 200-C., or in excess thereof, and pressures in the neighborhood of 200 pounds per square inch, or in excess thereof. Such oxyalkylations have been described in aforementioned U. S. Patent No. 2,499,370. Generally speaking, such procedure is employed under conditions Where there are more than three points of reaction per molecule, and where the amount of oxide added is comparatively high in ratio to the initial reactant. Such procedure is entirely satisfactory in the particular oxyalkylation step described in th instant part, i. e., Part 2.

However, since the amount of oxide is comparatively low, from approximately 2 moles per phenolic hydroxyl up to approximately 4 moles or slightly in excess thereof, it is apparent that time is. not a factor. In other words, it is just as satisfactory to employ a comparatively low temperature and lowpressure rather than conditions of oxyalkylation previously mentioned, which result 'v'olved, due to accident;

. in a; rapid reaction rate. For this reason I have employed conditions of the kind involving temperatures of about 9 5 to 115 'C., and pressures of to pounds. or less. If an atmosphere of inert gas, such as nitrogen, is present during a reactionneedless to say the pressures maybe some- Such low temperature; low reaction rate oxy'al- Kylations have been described very 'cornpletel'yfin U. S; Patent No. 2,448,664, to Fife et a1., dated. September 7, 1948, V

i previously indicated, low pressure, low temperature reaction rates may require' considerable time, as; for instance, in some of the subsequent e amples in the neighborhood of one to two hours. Actually, at 180 to 200 C., such reaction might be conducted in ten minutes'orless.

In large scale low temperature operations the time might be somewhat longer, for instance, 5

we; hours. In any event, the'reaction is so com-' paratively short, that it is of no marked significanoe, but-it is more convenient to use these lower temperatures on a laboratory or semi pilot plant scale.

QI'have' used conventional equipment with two added automatic features: (a) A solenoid-controlle'dvalvewhich shuts 'ofi the ethylene oxide in event that the temperature gets outside a predetermined and se't'range, for instance, 110 to 120 0,, and (b) another solenoid'valve which the ethylene oxide (orfor that matter prop mne, oxide if it isbeing used) if the'pressure "g'ets'beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employedior'this purposewhere the pressure of reaction ls' higher, speed of reaction is higher, and time of reaction is much shorter. For reasons which are 'obyious' in light of What has been said previously,

I have not found it necessary to use such automaticcontrols under the conditions of'oxyethylation employed in introducing such small portion of alkylene' oxide. Controls could beused, if desired, and certainly would be used in high temperature' oxylalkylations.

Thus, in preparing the various examples I have found it particularly advantageous to use laboratory equipment which is designed to permit'continuous oxyalkylation, whether it be oxypropylation or oxyethylation.

The oxyethylation procedure employed in the preparation of the oxyethylation derivative has Eeenuniform1y the same, particularly in light of the fact that either a continuous automaticallycontrolled procedure was employed, or else a short iron-automaticmethod is used. Indeed, in this instance, the latter is preferred. In this procedure the autoclave was a conventional autoclave "made of stainless steel and having a capacity of "approximately one gallon and a working pressure ,etuyrene oxide", tothe bottom of thefi 'utoolave smug with suitabledevices for both cooling and o her anaemia e c e sse. d es- 'Suchautoclaves are, of course, in essence scale" replicas of the usuaiconventional claveus'edinoxyalk ionp t instances; lar autq l 'wes'i M haying a capacity rangingthe neighborhood ma nt o Continuous-l operation-.101 supstantia y' ccr'it iit uous' operation, was achieved by the use ffa separate co tairier to hold thealkiyletie"dxidebemg e 'l'plo' g', ar'ticu1ariy et ylene oxide or idei Th co in c e W new of! 1?. tions between the b mb it was" required, ay-tug? usual ;c on"ventio'ri al procedure or addition-which provide -greater safety was used assume, such a's safety glass, r t s re p et ev....

In using small amounts of ethylene oxide iiiproximately 2 msiestr ethyleneoxidefper' lienolic hydroxyl on nee not inployithe 4 matic devioes unless de red. u os-laws of the kind describes arse fped withautoinatic conm siwh y lime w propylene oxide in evg'ant itempe e '01" reaction passes out'oi the predetermined" range, or pressiure in the" autoclave: pas es "out of; the predeterinine'd range, However, in procedure of th'e'k'ind herein reported, I have done nothing further than t et-the inlet ape'n o the oxidewas added inapproximatelythree hours and thenproceed to let the'autoclave run fdr'a' total of four hours. toinsure completeness' of reaction. ressures in no instance registered m'ore'than 30 o-"40 and the temperatures variedfrom to C.

One thing must-be borne in mind when operating at theseco'mparativelylow' temperaturesof oxyalkylation. When operating at a; comparatively high, temperature, jo'r instance; between to 20p" 'C an unreacte'd alkylene oxide, such s h le e 'pr pr en o lderm pr sence felt in the 'incre'asefin pressure 'o r' the consi'stenc'y'ofa high'fpr'essure; However; at a low enough temperature, it may happen that theoride, such*as propylene oxide, goes in as'a' liquid. If so, and if it: remains unreacted, there is, of course, an inherent dangerian'd appropriate steps must be takentosafeguard' against this possibility';' if need be, a sample must be withdrawn and examined for unreacted'propyleiie' oxide; or

time of reactioniis not apt to be a factor.

may vary from as little. as /2% up to 5%. The

amount may vary during the oxyalkylation period, as exemplified bythe addition of the catalyst at the very beginning of the reaction only and with no further addition. Needless to say, there is a comparatively high concentration of catalyst at the beginning of the reaction and a =.'comparatively low concentration at the-end; in

fact. not infrequently the amount of catalyst at the end will be one-half of 1% sodium methylate,

or caustic soda, or less. Catalyst can be added intermittently during the reaction period, provided suitable equipment is available. It is In the present situation, since comparatively little of the ethylene oxide wasadded per-phenolic hydroxyl (about .2 to 4 moles per hydroxyl) In other comparable oxyalkylations, as have been described in the literature, the amount of oxide added mightbe 50 to 100 times this amount. Under such circumstances, it is necessary to speed up ,the reaction in order to finish the process within a reasonable length of time; .In thepresent case the-amount of oxide added was so small that even using a low temperature (95 to 115 C.) ,.and a comparatively low -pressure,-less than 30 or 40 pounds maximum, the reaction was complete in a very short period of time. As a I convenience, I have generally added the oxide over a 3-hour to 8-hour period, since the apparatus was practically automatic. The amount of catalyst use was generallyabout 1.0% to 3.0%

of the initial resin. Somewhat more can beused, or slightly less. If more is used the reaction would, of course, be faster, and ifless is used reaction might be a little slower. I

One limitation ofv small-scale autoclave equipment (a .gallon to a 2-gal1on autoclave) is the diffidulty involved in a suitable automatic device j for adding a dry catalyst, such as sodium methyl- 'ate,' during the reaction. This presents no problem on a large scale with larger size equipment, and thus, thesame operation conducted in equipment of increased capacity means that all the catalyst need not be added at once, but can be added intermittently in a predetermined amount, based onan hourly rate, or based on the addition'of ethylene or propylene oxide. N For instance, in a large scale operation involving equipment having about twenty five times the capacity of the autoclave employed, arrangements were made to introduce better than .a gallon of ethylene or propylene oxide (4,000 grams) per hour, along with the introduction of 20 grams of sodium methylate hourly during the operation period.- The net result, as far as the final material was concerned, was the same, to wit, a residual alkaline catalyst.- equivalent to about I sodium n'iethylate.v

only being different. In the succeeding tables the ratherdiflicult to employ such equipment on a Q laboratory scale, but it can beemployed, of

-course, on a-pilot plant scale or larger scale.

the resin.

amount (if x ylene resin solution is shown by weight; subtracting 300 in each instance gives the weight of the resin. For purpose of calculation the alkylene oxide added and the original phenol employed in manufacture was used as a basis. This was more convenient than using the weight of resin obtained, because it may vary somewhat from batch to batch. One reason for using the original phenol as a base for calculation is that the claims and the hereto appended drawing, which in essence is part of the claims also, specifies the components in terms of the ethylene oxide to phenolic hydroxyl ratio. Actually, the amount was weighed on a laboratory balance which may have been inaccurate to the extent of A1 to This, of course, is immaterial in a procedure of the present type. Similarly, the ethylene oxide wasweighed as closely as possible, but here again the variation could have been /2% to 1%. 3- gram moles of the phenolwere used to provide The amount of. oxide employed is shown in the table. The amount of catalyst (s0- dium'methylate) employed is also shown... In all instances the temperature, as stated, was never higher than 115 C. and generally varied'from C. to C. The pressure was never higher than 40 pounds per square inch, and in all instances thereaction was complete in 3 to 8 hours.

Oxyethylation was conducted in the usual manner, first sweeping out the equipmentwith nitrogen and setting the controls as far as the addition of the oxide was concerned but ignoring the controls as far as temperature and pressure were concerned. Any adjustment required in the matter of temperature and pressure could be made manually by examination of the gauges a few times during the entire procedure. The next step was to add the ethylene oxide in such a manner that it was injected in the reaction vessel in somewhere between 2 to 2 hours andthen permitting the reaction period to extend up to 3 hours so as to be sure all the oxide. had combined. All the oxide had combined in this intance using a minimum amount of oxide. However, when the maximum amount of oxide was used the time period was more apt to befl5 to 6 hours if the final stirring period extended to 6 to 8 hours.

Specific examples are included by way of illustration, as follows:

Eazmnple 1b 486 grams of a resin of the kind described as Example 1a, of Patent 2,499,370, mixed with 300 grams of xylene were used as the initial charge. To this there were added 1.25% (about 6.5 grams) of sodium methylate. These ingredients were placed in the autoclave and the autoclave sealed and the automatic devices adjusted for injecting 291 grams of ethylene oxide in about 2 /2 hours. The reaction was continued for about 3% hours to be sure that it was complete. The ratio is 2.2 moles of ethylene oxide for each initial phenolic hydroxyl involved in resin manufacture. The temperature was approximately 110 C. and the pressure was less than 30 pounds per square inch. The final product was a viscous semi-resinous product being somewhat between a resin and a viscous amber-colored fluid obtained by increased oxyethylation. In such instances where the'resins employed were liquids, needless to say, further oxyalkylation was in the direction of reduced viscosity. Some resins which were pratically viscous liquids to start with became less viscous or more towards the liquid stage. The color Example 21) The same procedure was repeated, using the same amount of resin, a somewhat larger amount of catalyst (9 grams), and 436 grams ofoxide. This oxide was injected in a -hour period and then stirring continued for an hour longer..

Otherwise the operating conditions were the same as in Example 11), preceding. This oxide ratio represented 3.3 moles per phenolic hydroxyl.

Example 35 The same procedure was followed as in Example 1?: except that the amount of catalyst was larger, i. e., 12 grams. The amount of oxide injected was 582 grams, equivalent to 44 moles per phenolic hydroxyl.

Emam'ple 4b The same procedure was followed as in Example 1b, preceding, except that 528 grams of the resin identified as Example 3a, of Patent 2,499,370, were used instead 015486 grams of resin Example 10. in Example 1b. Similarly, the amount of xylene was the same, i. e., 300 grams. The amount of ethylene oxide was the same as in Example 11). The conditions of oxyethylation were the same as in Example 1b. The ratio of oxide to resin was the same as in Example ib, i. e., 2.2 moles per phenolic hydroxyl. The appearance of the final product was substantially the same as in Example 11).

Example -5b The same procedure was followed as inExample 2b, preceding, using resin of Example 3a of Patent 2,499,370. 528 grams of resin mixed with 300 grams of xylene were employed. 9 grams of catalyst were employed. 436 grams of ethylene oxide were injected. The time period was thesame as in Example 2b, preceding. The ratio of oxide to resin was the same as in Example 2b,'to wit, 3.3 moles per phenolic hydroxyl.

Example 6?) Example 7 b The same procedure was-followed as in Example lb, preceding, except that the resin employed was the one identified as Example 73a of Patent 2,499,370. The amount employed was 822 grams. This was mixed with 300 grams of xylene. The amount of catalyst employed was 8-grams. The conditions of reaction were substantially the same as in'Example la, of Patent 2,499,370. The amount of oxide was 291 grams. This represented a ratio of 22 moles per phenolic hyd exy Example 8b The same procedure was followed as in Ex: ample 2b, preceding, except that 822 grams of resin 73a of Patent 2,499,370 were employed instead of resin of Example 1a of Patent 2,499,370. The amount of oxide added was 436 grams. The amount of catalyst employed was somewhat larger, 13 grams; The conditions of reaction in all other respects were identical with that described in Example 22). The appearance of the -final product was much the same. The amount of oxide represented 3.3 moles per phenolic hydroxyl. Example 91) The same procedure was iollowed as i ample 3b, preceding, except that 822 gramsof resin of Example 73a of Patent 2,499,370 were used instead of resin of Example 1a of Patent 2,499,370. The amount of catalyst was some}. what larger, 16 grams.

The amount of oxide added was 582 grams. The time of reaction'an'd conditions of reaction were substantially the same as described in Example preceding. The appearance of the final product was much the same as in Example 3b, preceding. The amount of oxide employed represented 44 moles per phenolic hydroxyl.

The above examples illustrate definite ratio oxyethylation and the procedure is identical with that which has been described repeatedly in various patents. Needless to say. the oxyethylations could be conducted at a higher temperature in less time just as satisfactorily. This is purely a matter of choice and a matter of equipment available.

resins described in Part 2, preceding, can be freed from solvent by the usual procedure, i. e.,

"distillation and particularly vacuum distillation.

I-lloweven'as far asuse as demulsifiers is concernedII have foundfi't' more convenient simply to dilute the xylene solution to 50% by weight and then mix the xylene solutions to obtain the synergistic mixturesherein specified.

Reference is now made to the triangular graph of the ,heretoattached drawing. This is a 'conventional graph where each apex represents of the particular oxyethylated resin 'asjindicated. I have found that if mixtures are made of the three oxyethylated resins derived, of course, from thesame resin, and if such mix tures fall within the triangle A, B, C, then'and in that event such mixtures in many instances are at least 10% better than the comparable three ingredientsalone, or any mixture of two of the three ingredients. In other words there is a synergistic efi'ectinvolved, the exact nature of which is open to speculation. Obviously the preparation of such mixtures requires no description beyond the chart itself. Each of the three determining points represents 60% of one component and 20% each of the other two. A mixture of one-third each, of course, is right in the center of the defined area A, B, C. I have made samples of such mixtures by mixing the first three oxyethylated resins, i. e., 11), 2b,. and 31). Similarly, I have mixed the next three, i. e., 4b,.5b, and 6b; and also I have mixed the last series, 7b, 8b, and 9b. In each case a variety of mixtures are obtained, all of which fall within the, composition of the specified area 'A, B,. ,C.

Such mixtures are illustrated by the following examples:

alcohol, hexyl alcohol, 'octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents Percentage of 2.2 oxyethylation Percentage of 8.3 oxyethylation Percentage of 4.4 oxyethylation Prepared From 1b, 2b, and 3b..

Needless to say, comparable mixtures can be prepared on a solvent-free basis by using the undiluted components.

As has been stated elsewhere andspecified in the claims these mixtures are synergistically better than the components of the mixture either alone or in binary mixture. This ;does not mean that such mixtures as defined in the claims were invariably and inevitably better than the components alone, or in combination, on all oils but I have found in numerous instances that such superiority is at least 10% or more, and sometimes 15% or more. In many instances the superiority is not only quantitative but also qualitative, i. e., not only will the mixture demulsify a larger quantity of oil than the components alone or in binary mixture but will also demulsify the oil faster or at a lower temperature, giving a pipeline oil having less foreign matter. See booklet entitled "Treating Oil Field Emulsions, used in the Vocational Training Courses, Petroleum Industry Series of th American Petroleum Institute.

7 PART Conventional demulsifying agents employed in such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum,

etc., may be employed as diluents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing my process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion tobe treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification; procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. Insoinecases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, c. e., the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier-being added, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the well.- head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion separates and settles from the mass.

The following is a typical installation:

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the effluent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportio-ning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the fiowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the water level to drain off the water resulting from demulsification or accompanying the emulsion as free water, the other being an oil outlet at the top to permit the passage pf dehydr ed qiliil fl'aa second tank, being a storage tank, which holds 5 pipeline or dehydrated oil. If desired, the conduitor pipe which serves to carry thefiuids from the well to the settling tank mayincludea sectionof pipe with bafiles to serve as a mixento insure;

thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient-terns per-ature, for instance, to F., or both heaterand mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, -1 :5,000. As soon as a complete break or satisfactorydermulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just sufiicient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1110,000, 1:15,000, 1 :20,000, or the like.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 200, with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictatzd in part by economic considerations, i. e., cos

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier which in turn is a synergistic ternary mixture of three components, each of the three components being a hydrophile synthetic product; said hydrophile synthetic product being the oxyethylation product of (A) ethylene oxide, and (B) an oxyethylation-susceptible, fusible, organic solventsoluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; said oxyethylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (C2H40)n; in one of the three components 11. varies from 2.0 to 2.4 on a molal basis calculated on the original phenolic hydroxy; in the second component n varies from 3.0 to 3.6 on a molal basis calculated on the original phenolic hydroxyl; in the third component 11 varies from 4 to 4.8 on a molal basis calculated on the original phenolic hydroxyl; the phenolic and aldehydic reactants being identical in all three components; the combining ratios of the three components being determined by the triangiilar area of the graph in the hereto appended drawing as defined approximately by the triangle .A, B, C, said proportions being on aweight basis; and with the final proviso that said demulsifier be more effective than (1) any of the three components alone, or (2) any two of the three components in combination.

2. The process of claim 1 wherein the aldehyde is formaldehyde.

3. The process of claim 1 wherein the aldehyde is formaldehyde and the phenol is butylphenol.

4. The process of claim 1 wherein the aldehyde is formaldehyde and the phenol is amylphenol.

5. The process of claim 1 wherein the aldehyde is formaldehyde and the phenol is nonylphenol. 15

5 phenol.

MELVIN DE GROO'IE.

REFERENCES CITED The following references are of record in the 10 file of this patent:

UNITED STATES PATENTS De Groote et a1 Mar. '7, 1950 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER WHICH IN TURN IS A SYNERGISTIC TERNARY MIXTURE OF THREE COMPONENTS, EACH OF THE THREE COMPONENTS BEING A HYDROPHILE SYNTHETIC PRODUCT; SAID HYDROPHILE SYNTHETIC PRODUCT BEING THE OXYETHYLATION PRODUCT OF (A) ETHYLENE OXIDE, AND (B) AN OXYETHYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A 